Process for breaking petroleum emulsions



n d SFMQPWFTW 2,695,887 P t etsdN v- We This invention relates toprocesses or procedures particularly adapted for preventing, breaking orresolving emulsions ofthe water-in-oil type, and particularlypeitroleumemulsions.

The present invention is a continuation-in-part of my co-pendingapplications; ;Serial:Nos.-288,742, filed May 19, 19, 19'52, 296,08' 3-,filed June 27, 1952, and 301,803, filed'July 30 ,=1952.-

My invention provides an: economical and rapid process for resolvingpetroleum emulsions-of the waterinoil type, thatare commonly referred toas cut oil, roilyoil, emulsified oil,- etc., and whichcomprise-finedroplets of naturally-occurring .waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphaseofthe emulsion.

It also provides an economical and rapid process forseparating emulsionswhich have been -preparedunder controlled-conditionsfrom mineral oil,such ascrude oil andrelatively soft waters or-weakbrines, Controlledemulsification and subsequent demulsificat-ion under the conditionsjustmentioned are-of significant-value in removing impurities, particularlyinorganic salts, from pipe line oil.

The demulsifying" agents employed in the present demulsifying processarethe products-obtained by' the process of first condensing-la) anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble;low-stage phenolaldehyde-resin of thetype described hereinafter in Part 1; (b) a basic nonhydroX-ylatedsecondary monoamines havingnot more than 32. carbon atoms in any groupattached to the amino nitrogen atom, and (0) formaldehyde; saidcondensation reaction beingconducted at a temperature sufficiently highto eliminatewater and below the pyrolytic point of thereactantsandresultants of reaction; and with-the proviso that the-resinouscondensation product resultingfrom the process be heat-stable andoxyalkylation-susceptible. The condensation reaction is followed by anoxyalkylation step by means of an alpha beta alkylene oxide having not'tnore'than l carbon atoms and selected from'the' class consisting ofethylene oxide, propylene oxide,',butylene oxide, glycide andrnethylglycide to form the present demulsifyingagents.

In many instances and for various purposes,particularly for the""resolution" of petroleum emulsions of the water in-oil type, one maycor'n'b'inea comparatively lar'g'e 'pro portion of the alkylene oxide,particularly"propylene oxide or a combination of propylene oxide andethylene oxide, with a comparatively small proportion-of the resincon'densatezf Insom e"instances"the' ratio by weight has beenas'highi'asfiO-to-l, i. e.', the ulti'r'nate"product?'ofreactioncontained approximately 2% of resin condensate andapproximately"98% of alkylene"oxide'."

This invention in a more lirnited aspect as far as the reactantsare'concerned which are subjected to oxyalkylation are certain:amine-modified thermoplastic phenolaldehyde resins. Such amine-modifiedresins are described in the aforementioned co-pending applications andmuch that is said herein is identical with the text of saidaforementioned co-pending applications; however, somedetail is omittedsince the art is aware of these resinsthrough my mentionedcope'nding'application,- e. g-., 'S'. N. 296083. For purpose ofsimplicity the invention," purely from a standpoint of'theresin'condensate 'involved,mayi- 1 be exemplified by an idealized formula asfollows:

in which R represents an aliphatic hydrocarbon subtime stituentgenerally having 4 and not-'over'18 carbon atoms butmost preferablynotover' 14 carbonatoms; and it generally is a small whole numbervaryingfrom 1 to 4. In-the resin structure it is shown as bein'g'derived-from formaldelhyde althoughobviously otheraldehydesareequally'satisfactory. The amine residue in the abovestructure is derived from a basic amine,- and usually-a strongly basicamine, and may be indicated thus in which R represents any appropriate"hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl1"adical,"etc., free from hydroxyl radicals. The only limitation is thatthe radical should notbe'a negative radical, which'coi1'-" siderablyreduces the basicity of the amine,"such asan' aryl radical or an acylradical. Needless to say, the two occurrences of R"may jointly representa single divalent radical instead oftwo mon'ov'alent radicals; This isillu's' trated byrnorp'holine and piperidine. The introduction of twosuch amino'radic'als into a comparativelysmall' resin molecule, forinstance, one having 3 to 6 phenolic nuclei as specified, alters theresultant'pro'duct 'ina number of ways. Inthe first place, a basicnitrogen atom, of" course, adds -a hydrophileefiect; in the secondplace," depending on'the size 'of the 'radicalR, tl'iei'efrnay'beacounterbalancing'hydrophobeeffector one inwh'icli the'hydr'ophobe effectmore than 'counterbalanc'es the hy-" drophile effect of thenitrogenatom. Finally, in such cases wn reR' contains one ormoreoxygenatoms, another effect is introduced, particularly anothe'r'hydrophil'e'ef feet.

I amnot aware that'it has been'prev'iously suggested to modify byoxyalkyl'ation the resin'condensates"of"thekind-described herein and inmy'copendinglapplication' S. N. 269,083. Thecondensationproductobtained"ac'-" cor'ding to the presentinventio'nis heat stableand," in'fact, one of its outstandingqualities is that it .canbe subjected tooxyalkylation, particularly oxyethylationor' oxypropyl'atio'n, underconventional conditions, i. e., presence of an alkaline catalyst, forexample, but in any event at a temperature above C. without bec'o'm'ingan insoluble mass.

Any reference, as in the hereto appended claims, to the procedureemployed in the process is not intended to limit the method or order inwhich the reactants are added, comm'in'gled or'reac'ted. The procedurehas been referred to as a condensation'process for obvious'reasonsf Aspoint'ed out elsewhere'it is my preference to'dissolve the resin in asuitable solvent, add the amine, and then add'the formaldehyde as a 37%solution. However, all thre'ereactants' can be addedin any order. I aminclined to believe'that in the presence of a basic catalyst, such asthe amineemp'loyed, that the formaldehyde produces methylol groups.attached to 'the' phenolic nudleiwhi'h', intur'n; 'react-Withthe amine.It wouldbei'rnmaterial, of course, if the formaldehyde 'reacted'with'the'ami'ne soas to introduce a methylol group attached't'o' nitrogenwhich, in turn, would react with the resin molecule. Also, it wouldbeimmaterial ifboth' types of compounds were formed which reacted witheach other with the evolutior'r'of a mole'of' formaldehyde availableforfurther reaction. Furthermore, a reaction could take place in whichthree different molecules aresimultaneously in-' volved although; fortheoretical reasons, that is less likely. What is said herein in thisrespect is simply by'way of explanationto avoidanydirnitati'on inregard'to the appended claims. I

Since theami'nesherein employed are nonhydrox'ylat'ed it is obvious-theamine mo'dified"resin is susceptible to oxyalkylation' by virtue of thephenolic hydr'oxyl radicals. Referring to the "idealized formula whichappeared previou'sly it is obvious the 'oxyalkylated"derivativesfor'atleast a substantial portion of them, could be indicated in the followingmanner:

in which R"O is the radical of alkylene oxide, such as the ethoxy,propoxy or similar radicals derived from glycide, ethylene oxide,propylene oxide, or the like, and n is a number varying from 1 to 60,with the provlso that one need not oxyalkylate all the availablephenolic hydroxyl radicals. In other words, one need only convert twophenolic hydroxyl radicals per resin molecule. Stated another way, n canbe Zero as well as a whole number subject to what has been saidimmediately pre: ceding, all of which will be considered in greaterdetail subsequently.

As far as the use of the herein described ultimate products goes forpurpose of resolution of petroleum emulsions of the water-in-oil type, Iparticularly prefer to use those which as such merely as a result ofoxyalkylation alone or in the form of the free base or hydrate, i. e.,combination with water or particularly in the form of a low molalorganic acid such as the acetate or hydroxy acetate, have sufficientlyhydrophile character to at least meet the test set forth in U. S. PatentNo. 2,499,368, dated March 7, 1950, to De Groote et al. In someinstances oxyalkylation is the controlling factor rather than the basicnitrogen atoms present regardless of their structure or combination. Insaid patent such test for emulsification using a water-insolublesolvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated condensation productsas such or in the form of the free base or in the form of the acetate,may not necessarily be xylene-soluble although they are in manyinstances. If such compounds are not xylene-soluble the obvious chemicalequivalent or equivalent chemical test can be made by simply using somesuitable solvent, preferably a water-soluble solvent such as ethyleneglycol diethylether, or a low molal alcohol, or a mixture to dissolvethe appropriate product being examined and then mix with the equalweight of xylene, followed by addition of water. Such test is obviouslythe same for the reason that there will be two phases on vigorousshaking and surface activity makes its presence manifest. It isunderstood the reference in the hereto appended claims as to the use ofxylene in the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368 dated March 7, 1950,to De Groote and Keiser. In said immediately aforementioned patent thefollowing test appears:

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-surface-active stage. The surface-active properties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis as follows: The oxyalkylated resin is dissolved in an equal weight ofxylene. Such 50-50 solution is then mixed with 1-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-in-water type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awaterin-xylene emulsion (water-in-oil type) which is apt to reverse onmore vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4 /2 units per resin molecule. Such resin, when diluted with anequal weight of xylene, will serve to illustrate the aboveemulsification test.

In a few instances, the resin may not be sufficiently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that such mixture, or any othersimilar mixture, is considered the equivalent of xylene for the purposeof this test.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With borderline cases, i. e., those whichshow only incipient hydrophile or surface-active property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. The fact that a reagent is capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can be made with thebutylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxidehave been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may maskthe point at which a solventfree product on mere dilution in a test tubeexhibits selfemulsification. For this reason, if it is desirable todetermine the approximate point'where self-emulsification begins, thenit is better to eliminate the xylene or equivalent from a small portionof the reaction mixture and test such portion. In some cases, suchxylene-free resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientself-emulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added water-insoluble solvent and minor proportionsof common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it is really immaterialwhether a xylene solution produces a sol or whether it merely producesan emulsion.

For convenience, the subsequent text will be divided into five parts.

Part 1 is concerned with the general structure of the amine-modifiedresin condensates and also the resin itself, which is used as a rawmaterial.

Part 2 is concerned with appropriate basic secondary monoamines freefrom a hydroxyl radical which may be employed in the preparation of theherein described amine-modified resins or condensates;

Part 3 is concerned with the condensation reactions involving the resin,the amine, and formaldehyde to produce the specific products orcompounds;

Part 4 is concerned with the oxyalkylation of the products described inPart 3, preceding; and

Part 5 is concerned with the use of the oxyalkylated amine-modifiedresins obtained as described in Part 4, preceding, for use in theresolution of emulsions of the water-in-oil type.

In the subsequent text, Parts 1, 2 and 3 appear in substantially thesame form as in the text of the aforementioned co-pending applications,Serial Nos. 288,742, filed May 19, 1952; 296,083, filed June 27, 1952;and 301,803, filed July 30, 1952. Furthermore, Part 4 is essentially thesame as Part 4 in the last aforementioned co-pending application, i. e.,Serial No. 301,803, filed July 30, 1952.

PART 1 It is well known that one can readily purchase on the openmarket, or prepare, fusible, organic solvent-soluble, water-insolubleresin polymers of a composition approximated in an idealized form by theformula OOH% I OBI-13:1 OH H H R R n R In the above formula n representsa small whole number varying from 1 to 6, 7 or 8, or more, up toprobably 10 or 12 units, particularly when the resin is subjected toheating under a vacuum as described in the literature. A limitedsub-genus is in the instance of low molecular weight polymers where thetotal number of phenol nuclei varies from 3 to 6, i. e., n varies from 1to 4; R represents an aliphatic hydrocarbon substituent, generally analkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl,hexyl, decyl or dodecyl radical. Where the divalent bridge radical isshown as being derived from formaldehyde it may, of course, be derivedfrom any other reactive aldehyde having 8 carbon. atoms or less.

Because a resin is organic solvent-solubledoes-not mean soluble in'anonoxygenated solventi such asbenzene, or

Xylene, but requires an oxygenatedisolventsuoh.as a low molalalcohol,.dioxane, or. diethylglycol- .diethylether.

Sometimes 1a miXtureof.-the two solvents (oxygenated:

and -no'noxygenated) 'will servew SeeExample 9a of U. S. PatentN'.2,499,365T, dated March --7, 1950, to DeGroote and. :Keiser.

The resins'hereinemployed :asfraw'materials mustbe soluble in anonoxygenated solvent, such as-benzene or Xylene. Thispresents noproblem-'insofarthat all that is .required is to make Ia solubility teston commercially available resins',.or elseprepareresins which are xyleneorbenzene-solubleias described in aforementioned U. S. Patent No.-2,499,365, or in.U.-. S. Patent No. 2,499,368 dated March. 7, 1950, toDe Groote andKeiser. In said patents there are describedoxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resinshaving an average molecular weight'corresponding to at least 3 andnotov'er'6 phenolic nuclei per resin molecule. Thephenol aldehyde'resinsare difunctional only in'regard to methylol-forming reactivity, andtheresins are' derived 'by reaction between a difunctional inonohydricphenol and an aldehyde having'not over 8 carbon atomsand' reactivetoward the phenol. Also, the resins are formed in the substantialabsence of trifunctional phenols. The phenol constituent of the resinsis of the formula in which R is an'aliphatic hydrocarbon radical havingat'least 4 carbon atoms and not more than 24 carbon atoms andsubstituted" in the2, 4, 6 position.

Ifone selected a resin of the kind .just described previously. andreacted approximately one mole of the resin With two moles offormaldehyde and two moles of a basic nonhydroxylated secondaryamine asspecified, following the same idealized oversimplification previouslyreferred to, the resultant'product might be illustrated R R R The basicamino may be. designated thus:

RI BN lit ih i As has been pointed out previously, as far as the resinunlt goes one can use a mole of aldehyde other than formaldehyde, suchas\acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplinR R R R 'ILR in which R is the divalent radical .obtainediromthe.

particular aldehyde employed .to form theresin. For reasons which areobvious the condensation'product.obr

tained appears to be described best in terms of the method.

of manufacture.

As previously stated the preparation of. resins, the kind.

herein employed as reactants, is well. known. See prev Resins canviously mentioned U. S. Patent. 2,499,368. be made using an acidcatalyst .or basic catalyst ora catalyst having neither acid norbasioproperties in theordinary sense or Without any catalystat all. It[is preferable that the resins employed be substantially neutral.

in other words, if prepared by using a strong acidtas. a catalyst, suchstrong acid should beneutraliz'ed. Siiiii larly, if a strong base isused as a catalyst .it .is preferable that the base be neutralizedalthough I have found that sometimes the reaction described proceededmore rapidly in the presence of a small amount of a. free. base. Theamount may be as small as a .200th.of a ercent.

and as much as a few 10ths of a percent. Sometimes, moderate increase incaustic soda and caustic -potashmay be used. However, the most desirableprocedure in practically every case is to have the resin neutral.

In preparing resins one does-not get'a single polymer, 1. e., one havingjust 3 units, or just'4 units, or just 5 units, or ust 6 units, etc; Itis usually a mixture; for mstance, one approximating 4 phenolic nucleiwill have some trnner and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture ofthe resins I foundnoreason for using otherthan those which are lowest in. prices and most readily availablecommercially. For purpose of convenience suitable resins arecharacterized in the following table:

TABLE I 1/ Mol-swt: R f fi R ggf n of resin molecule Phenyl Para...Formaldehyde. 3. 5 992. 5

Tertiary butyl... .:.do 1o 3. 5 882.5 Secondary butyl. 3.5 882.5Oyclohexyl 3. 5 1,025. 5 Tertiary amyL... 3.5 959.5 Mixed secondary 3. 5805.5

and tertiary amyl.

Propyl 3. 5 805. 5 Tertiary her 3. 5 1, 036. 5 Octyl. 3. 5 1, 190. 5Nonyl 3. 5 1, 267. 5 Decyl. 3. 5 1, 344.5 Dodecyl .110; 3. 5 1, 498. 5Tertiary butyl". do Acetaldehyde. 3.5 9455 Tertiary arnyL... .do do 3.51,022.5 Nonyl .d0 .d0 3.5 1,330.5 Tertiary butyl". do Bkutgrald'e- 3.51,071.5 Tertiary amyl.. 3. 5 1, 148. 5 Nonyl 3.5 1,456. 5 Tertiarybutyl. 3. 5 1, 00815 Tertiary amyL. 3. 5 1, 085.5 Non 3. 5 1, 393. 5Tertiary butyl 4. 2 996. 6 Tertiary amy1 4. 2 1, 083.4 Nonyl 4.2 1,430.6 Tertiary butyl. 4.8 1, 094.4

Tertiary amyl 4.8 1,189.6 Nonyl 4. 8 1, 570. 4

7 PART 2 As has been pointed out previously, the amine herein employedas a reactant is a basic secondary monoam ne, and preferably a stronglybasic secondary monoarmne, free from hydroxyl groups whose compositionis indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicaland may be heterocyclic in a few instances as in the case of piperidineand a secondary amine derived from furfurylamine by methylation orethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines suchas dimethylamine, methylethylamine, diethylamine, dipropylamine,ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine,and dinonylamine. Other amines include bis(1,3-dimethylbutyl)amine.There are, of course, a variety of primary amines which can be reactedwith an alkylating agent such as dimethyl sulfate, diethyl sulfate, analkyl bromide, an ester of sulfonic acid, etc., to produce suitableamines within the herein specified limitations. For example, one canmethylate alpha-methylbenzylamine, or benzylamine itself, to produce asuitable reactant. Needless to say, one can use secondary amines, suchas dicyclohexylamine, dibutylamine or amines containing one cyclohexylgroup and one alkyl group, or one benzyl group and one alkyl group, suchas ethylcyclohexyl amine, ethylbenzylamine, etc.

Another class of amines which are particularly desirable for the reasonthat they introduce a definite hydrophile effect by virtue of an etherlinkage, or repetitious ether linkage, are certain basic polyetheramines of the in which x is a small whole number having a value of 1 ormore, and may be as much as 10 or 12; n is an integer having a value of2 to 4, inclusive; 111 represents the numeral 1 to 2; and m represents anumber to 1, with the proviso that the sum of in plus in equals 2, and Rhas its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature andparticularly in two United States patents, to wit, U. S. Nos, 2,325,514,dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944,

to Spence. The latter patent describes typical haloaklyl ethers such as01130 C2H4C1 GET-CH2 Hg CH-CH2O C2H4OC2H4B1 Such haloalkyl ethers canreact with ammonia, or with a primary amine such as methylamine,ethylamine, cyclohexylamine, etc., to produce a secondary amine of thekind above described, in which one of the groups attached to nitrogen istypified by R. Such haloalkyl ethers also can be reacted with ammonia togive secondary amines as described in the first of the two patentsmentioned immediately preceding. Compounds so obtained are exemplifiedby Other somewhatsimilar secondary amines are those of the compositionR-O(CHz)s as described in U. S. Patent No. 2,375,659, dated May 8, 1945,to Jones et al. In the above formula R may be methyl, ethyl, propyl,amyl, octyl, etc.

Other amines can be obtained from products which are sold in the openmarket, such as may be obtained by alkylation of cyclohexylmethylamineor the alkylation of similar primary amines, or, for that matter, aminesof the kind described in U. S. Patent No. 2,482,546, dated September 20,1949, to Kaszuba, provided there is no negative group or halogenattached to the phenolic nucleus. Examples include the following:beta-phenoxyethylamine, gamma-phenoxypropylamine,beta-phenoxyalph-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No.456,517 and may be illustrated by The products obtained by the hereindescribed processes represent cogeneric mixtures which are the result ofa condensation reaction or reactions. Since the resin molecule cannot bedefined satisfactorily by formula, although it may be so illustrated inan idealized simplification, it is difficult to actually depict thefinal product of ilfie cogeneric mixture except in terms of the processitse Previous reference has been made to the fact that the procedureherein employed is comparable, in a general way, to that whichcorresponds to somewhat similar derivatives made either from phenols asdifferentiated from a resin, or in the manufacture of aphenol-aminealdehyde resin; or else from a particularly selected resinand an amine and formaldehyde in the manner described in Bruson PatentNo. 2,031,557 in order to obtain a heat-reactive resin. Since thecondensation products obtained are not heat-convertible and sincemanufacture is not restricted to a single phase system, and sincetemperatures up to C. or thereabouts may be employed, it is obvious thatthe procedure becomes comparatively simple. This procedure is noted inmy copending application S. N. 296,083, and further description ofcertain details is unnecessary.

Needless to say, as far as the ratio of reactants goes I have invariablyemployed approximately one mole of the resin based on the molecularweight of the resin molecule, 2 moles of the secondary amine and 2 molesof formaldehyde. In some instances I have added a trace of caustic as anadded catalyst but have found no particular advantage in this. In othercases I have used a slight excess of formaldehyde and, again, have notfound any particular advantage in this. In other cases I have used aslight excess of amine and, again, have not found any particularadvantage in so doing. Whenever feasible I have checked the completenessof reaction in the usual ways, including the amount of water ofreaction, molecular weight, and particularly in some instances havechecked whether or not the end-product showed surface-activity,particularly in a dilute acetic acid solution. The nitrogen contentafter removal of unreacted amine, if any is present, is another index.

In the light of what has been said previously, little more need be saidas to the actual procedure employed for the preparation of the hereindescribed condensation products. The following example will serve by wayof illustration:

Example 1b The phenol-aldehyde resin is the one that has been identifiedpreviously as Example 2a. It was obtained from a paratertiary butylphenol and formaldehyde. The resin was prepared using an acid catalystwhich was completely neutralized at the end of the reaction. Themolecular weight of the resin was 882.5. This corresponded to an averageof about 3 /2 phenolic nuclei, as the value for n which excludes the twoexternal nuclei, i. e., the resin was largely a mixture having 3 nucleiand 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei.The resin so obtained in a neutral state had a light amber color.

9 -.8.82..grams.of .the. resin: identified-as 2a,.preceding werepowderedand mixed withan equal weight ofxylene, i. e., ..882. grams. Themixture was refluxednntil solution was 116 step is, of course, the sameasthe oxypropylation step nsofar that two .low boiling liquids arehandled in each instance. What immediately follows refers tooxyethylacong gletg. Itdw1aZ6then adjustgdflto approximately 30 tion andit is understood that oxypropylation can be i to an grams of -ie ylamineadded. The handled conveniently in exactly the. same-manner. mixture wasstirred vigorouslyrand formaldehyde added The oxyethylation procedureemployedin the preparaslowly. .The formaldehyde: wasused as a 37%solution tion 'of derivatives of the preceding intermediates has ead 162' gramswere employed, wh ch. were. added in been uniformly the-same,particularly in lightot the fact :11 out Arbours. The mixture wasSill-EH39 vigoro usly and that a continuous operating procedure wasemployed 'In kept. Within a. temperature rangeof 3( to 45 for thisparticular procedure the autoclave was a conventional .iabftfut 210hours. At the end of this period of time it was acketed autoclave, madeof stainless steel and having a I re uxe us ng .a phase-s eparating.trapand a small. amount capacity of approximately 25 gallons, and a workingpres- 0; aqueous distillate withdrawn. from time to time, and sure of300 pounds. gauge pressure. The autoclave was i t e presence ofunreactedformaldehyde noted. Any un; equippedwith the COIIVClltlOIlflLdevices and openings, such flialcltgcifigimeagilgdevseemet:,5) dxappear-7113111111 5 to 15. is tl hebzartiabslgostfieelglslt/ilrretrhoperatintgat spleeds1 iigam 50 g ass ar e s-.s00n.as eo or oo er-rnome er we an ermotormaldehydewasno longer; detectable thephase-separatcouple for recorder controller; emptying outlet, pressureing trap was setj-so as to eliminate. all. water ofi-solutiori gauge,manual and rupture disc vent lines; charge-hole for and reaction. Afterthe water was eliminated apart of initial reactants; at least oneconnection-for conducting the xylene was removed lll'ltll thetemperature reached the incoming alkylene oxideysuch asethylene oxide to;.approx1mately: -145 'C., or slightly higher. The mass the bottom otthe autoclave; along with suitabledevices ---was :kept at this highertenperature for about 4 hours for both cooling and heatingvthe autoclavethrough the and reacltniorti1 stopped.b iliuringt thisftnnetanyalclldiltlicilnag acllret. Also, I C lirglfetr ClfllS invadditilcjiln'.tfhereito,with thlel i wa er, W ic was pro a y-wa er 0reac ion w ic a cm s. so arrange a t ey are suita e or eating witformed, was eliminated by means'of the trap. The residual steam orcooling with water, andthe jacket further xyleliie was .permittled to'stay in the cogeneric mixture. A :equipped with electricalheating'devices,.such as are em- -sma amount of t e sample was'heated on a waterbath ployed for hot oil or Dowtherm systems. -Dowtherm, to remove theexcess xylene and the residual material more specifically Dowtherm A, isa colorless-non-corgasd dark reld in color anltll had the consistency ofa sticky rosive liquid consisting of an eutectic mixturesof diphenyl uior tac y resin. :T eoverall time for the reaction and diphenyl oxide.Such autoclaves are, ofcourse, in was about 30 hours In other examplesit varied from essence, small scale replicas of the usual conventional24 to 36 hours. Time can be reduced by cutting low autoclave usedzincommercial oxyalkylatingprocedure. terlrgiigatifige perirodgltouagplrfxnnatetg 3 to 6 hlours. Ct OI1t1Illl0lli Op6(11 alt31O11i10rsubsftantially ttzontinuous opin a e 0 owing ere are a arge numera ion,.18 ac ieve y e-use o a separa e con inner to "her of addedrexa nplesillustratingthesame procedure. hold the alkylene oxide being employed,particularly :Infeacih izase ttheinitital ln?%lg'6t'WiS0 St1gd.fand heldetlbiylene- OXIIJdC. bFlhe container consistfs essentially of a as anyow empera ure 0 or. a perio a ora ory om aving a capacity-o 21 out 10 to15 ot several hours. Then: refluxing was employed until the gallpns orewh t i excess th f, Thi -b b f lg y PP After odor of equipped, also,with an inlet for charging, and an outlet formaldehyde dlsapperalied thephase'separatmg trap W tube going to the bottom ofthecontainerso-as:to-:permit gmlvloyeg to sieparateitit allflthte1 Watt?i d l j 501mm}: discharging of alkylene oxide in theliquid'phase to then 9 cnsalon' er a a aertsepa autoclave. Other conventional equipmentconsists, of

rated enough xylene wastaken out to have the final prod- (nurse, of themtum disc ressure au 6 Si ht f d 1 not reflux fortseveral hoursrsomewherein therange of th t p g ee g -145 to 150 C., or. thereabouts; Usuallythe. mixture 45 ermome connec Ion 'Or m rogen or prqssurmg yielded aclear solution by-the time the bulk of the water, g g; fi gg s g g 3duntngluse c'or'all'ofthe water "had been'removed. e cfmnec 1on5 W en 5Om e an ave Note mataspimed outpreviously,vthistpl-ocedure i wereflexible stainless hose or tubingso that continuous in t t dby 24 1 j Tbl II, weighings could be .made Without breaking or making TABLE IIstrength of Reac- -Reac-' Max. EX R i A t A d d t gfi j Solvent used'tion tion distill. NO used gm mule use an amoml y andamt. temp., timetemp,

spin. and o 0 (hrs a C amt.

882 Diethylamine, 146 grains 162 y 882 20-25 30 150 480 Diethylamine, 73grains. J 70, 2- y 5 22-30 24 152 v(333 o 30%, 100 g; Xylene, 633 g.21-24 38 147 441 Dibutylamine,129 grams y 441 25-37 Y 149 .480 .do (1Xylene, 480 g. 20-24 35 149 a g as: a '882 1\ Ir a 87W 1 a: as a a O a a0 e Y a 473 Dioctylainine (di-2-cthy1hexy1amine), 117 grams 30%, 100 gXylene, 473 g. 20-21 38 148 e geare a ta 22 as 66" d ai iaa aa saaaaasare a 2- 5a: a a;

2 rams 1 o y s (ciniociaiociniimn, 250 grams 37%, 81g Xylene, 595 g.23-28 25 145 441 (O4H9OCH2CH(CH3)O(CH3)CHCH2)2NH, 0 Xylene, 441 g. 21-2324 151 480 (OiHsOOHaOEHOHz)O(CH3)CHCH2);NH, 361 grams .do Xylene, 480 g.20-24 24 150 511 toimooniomom ownaononamn, 361 gram 30% g Xylene, 511 g.20-22 v25 14s '49s '(CHKOGHZCHZOCH2CH20CH2CH2)2NH, 309 grains 81 gXylene, 498 g. 20-25 24 542 (CHsOCH2CH2OOH2CEzOCH2CH2)zNH, 309 grams (10Xylene, 542 g. 28-38 30 142 .547 (CH3OCH CH2OCHzCHzOCHzGHzhNH, 309 gramsdo Xylene, 547 g. 25-30 26 148 441 (CH3OCH2CH2OH2CH2CH2CH2)2NH, 245grams d0 t. Xylene, 441 g. 20-22 28 143 595 (C11 0CHzCHzCHflHrOHzCHzhNH,245 grams. 30%,100 g Xylene, 595 g 18-20 25 146 391 (SE30ongon omononnmn,9s grams W 30%, 50 g Xy1ei1e,391g 19-22 '24 145 PART 4 Inpreparing oxyalkylated derivatives of products of the kind which appearas examples inPart 3, I have found itparticularly advantageous to uselaboratory equipment *which permits continuous oxypropylation andoxyethylation. More specific reference will be made to treatment'with'glycide subsequently in the text. The .oxyethylation 85ethylations became uniform in that the reaction temperature could beheld within a few degrees of any selected point in this particularrange. In the early stages where the concentration of catalyst is highthe temperature was generally set for around 130 C. or thereabouts.Subsequently the temperature may be somewhat higher for instance, 135 to140 C. Under other conditions definitely higher temperatures may beemployed, for instance 170 C. to 175 C. It will be noted by examinationof subsequent examples that this temperature range was satisfactory. Inany case, where the reaction goes more slowly a higher temperature maybe used, for in stance, 140 C. to 145 C., and if need be 150 C. to 160C. Incidentally, oxypropylation takes place more slowly thanoxyethylation as a rule and for this reason I have used a temperature ofapproximately 135 C. to 140 C., as being particularly desirable forinitial oxypropylation, and have stayed within the range of 130 C. to135 C. almost invariably during oxypropylation. The lesser reactivity ofpropylene oxide compared with ethylene oxide can be offset by use ofmore catalyst,

more vigorous agitation and perhaps a longer time period. The ethyleneoxide was forced in by means of nitrogen pressure as rapidly as it wasabsorbed as indicated by the pressure gauge on the autoclave. In casethe reaction slowed up the temperature was raised so as to speed up thereaction somewhat by use of extreme heat. If need be, cooling water wasemployed to control the temperature.

As previously pointed out in the case of oxyproplation as differentiatedfrom oxyethylation, there was a tendency for the reaction to slow up asthe temperature dropped much below the selected point of reaction, forinstance, 135 C. In this instance, the technique employed was the sameas before, that is, either cooling water was cut down or steam wasemployed, or the addition of propylene oxide speeded up, or electricheat used in addition to the steam in order that the reaction proceededat, or near, the selected temperatures to be maintained.

Inversely, if the reaction proceeded too fast regardless of theparticular alkylene oxide, the amount of reactant being added, such asethylene oxide, was cut down or electrical heat was cut off, or steamwas reduced, or if need be, cooling water was run through both thejacket and the cooling coil. All these operations, of course, aredepending on the required number of conventional gauges, check valves,etc., and the entire equipment, as has been pointed out, is conventionaland, as far as I am aware can be furnished by at least two firms whospecialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory or semi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing: ,(a) If prepared from glycerol mono-chlorohydrin,

this product should be comparatively pure; (b) the glycide itself shouldbe as pure as possible as the effect of impurities is difficult toevaluate; (c) the glycide should be introduced carefully and precautionshould be taken that it reacts as promptly as introduced, i. e., that noexcess of glycide is allowed to accumulate; (d) all necessaryprecautions should be taken that glycide cannot polymerize per se; (6)due to the high boiling point of glycidc one can readily employ atypical separatable glass resin pot as described in U. S. Patent No.2,499,370, dated March 7, 1950, and offered for sale by numerouslaboratory supply houses. If such arrangement is used to preparelaboratory scale duplications, then care should be taken that theheating mantle can be removed rapidly so as to allow for cooling; orbetter still, through an added opening at the top, the glass resin potor comparable vessel should be equipped with a stainless steel coolingcoil so that the pot can be cooled more rapidly than mere removal ofmantle. If a stainless steel coil is introduced it means thatconventional stirrer of the paddle type is changed into the centrifugaltype which causes the fluids or reactants to mix due to swirling actionin the center of the pot. Still better, is the use of a laboratoryautoclave of the kind previously described in this part of the text, butin any event, when the initial amount of glycide is added to a suitablereactant, such as the herein described amine-modified phenol-aldehyderesin, the speed of reaction should be controlled by the usual factors,such as (a) the addition of glycide; (b) the elimination of externalheat, and (0) use of cooling coil so there is no undue rise intemperature. All the foregoing is merely conventional but is includeddue to the hazard in handling glycide.

Although ethylene oxide and propylene oxide may represent less of ahazard than glycide, yet these reactants should be handled with extremecare. One suitable procedure involves the use of propylene oxide orbutylene oxide as a solvent as well as a reactant in the earlier stagesalong with ethylene oxide, for instance, by dissolving the appropriateresin condensate in propylene oxide even though oxyalkylation is takingplace to a greater or lesser degree. After a solution has been obtainedwhich represents the selected resin condensate dissolved in propyleneoxide or butylene oxide, or a mixture which includes the oxyalkylatedproduct, ethylene oxide is added to react with the liquid mass untilhydrophile properties are obtained, if not previously present to thedesired degree. Indeed hydrophile character can be reduced or balancedby use of some other oxide such as propylene oxide or butylene oxide.Since ethylene oxide is more reactive than propylene oxide or butyleneoxide, the final product may contain some unreacted propylene oxide orbutylene oxide, which can be eliminated by volatilization ordistillation in any suitable manner. See article entitled Ethylene oxidehazards and methods of handling, Industrial and Engineering Chemistry,volume 42, No. 6, June 1950, pp. 12514258. Other procedures can beemployed as, for example, that described in U. 5. Patent No: 2,586,767,dated February 19, 1952, to \Vilson.

Example 10 The oxyalkylation-susceptible compound employed is the onepreviously described and designated as Example lb. Condensate 1b was inturn obtained from diethylamine and the resin previously identified asExample 2a. Reference to Table I shows that this particular resin isobtained from paratertiarybutylphenol and formaldehyde. 10.56 pounds ofthis resin condensate were dissolved in 8.8 pounds of solvent (xylene)along with one pound of finely powdered caustic soda as a catalyst.Adjustment was made in the autoclave to operate at a temperature ofapproximately C. to C., and at a pressure of about 15 to 20 pounds.

The time regulator was set so as to inject the ethylene oxide inapproximately three hours and then continue stirring for a half-hour orlonger. The reaction went readily and, as a matter of fact, the ethyleneoxide could have been injected in less than an hours time and probablythe reaction could have been completed without allowing for a subsequentstirring period. The speed of reaction, particularly at the lowpressure, undoubtedly was due in a large measure to excellent agitationand also to the comparatively high concentration of catalyst. The amountof ethylene oxide introduced was equal in weight to the initialcondensation product, to wit, 10.56 pounds. This represented a molalratio of 24 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was2112. A comparatively small sample, less than 50 grams, was withdrawnmerely for examination as far as solubility or emulsifying power wasconcerned and also for the purpose of making some tests on variousoil-field emulsions. The amount withdrawn was so small that nocognizance-of this fact is included in the data, or subsequent data, orin the data presented in tabular form in subsequent Tables III and IV.

The size of the autoclave employed was 25 gallons. In innumerablecomparable oxyalkylations I have Withdrawn a substantial portion at theend of each step and continued oxyalkylation. on a partial residualsample. This was not the case in this particular series. Certainexamples were duplicated as hereinafter noted and subjected tooxyalkylation with a diflierent oxide.

Example 2c This example simply illustrates the further oxyalkyl'ation ofExample lc, preceding. As previously stated, the oxyalkylationsusceptible compound, to wit, Example lb, present at the beginning ofthe stage was obviously the same as at the end of the prior stage(Example 10), to wit, 10.56 pounds. The amount of oxide present in theinitial step was 10.56 pounds, the amount of cata- 13 v lystmemained thewsame, totwit,=:one:; pound, --and=.the amount .of solvent remainedmthesame. i .The; amountof oxide added-Was another 1.9.56-pounds, alladditionaof oxide in these various stagesrbeingsbased;on thena'ddition*(Jf thisxpartieular amount. .Thus, at the end;ofz-the: oxyaethylationstep the amount-of oxideadded was Jatotalof .'21.12 pounds :andthermolal. ratio of ethylene oxide to resin condensate-was 48; to 1.Thetheoretical molecular we'ightwas 3168.

The 7 maximum temperature during .the operation was 125 C.:to -130 C.The:maximumpressurewasdnz-the 'rrange. of .15 .topounds. -..'-1"he timeperiod was 3 /2 :hours.

Example 3c Example 40 :The .oxyethylation. was continued. and theramount:of oxide-added again was 10.56 pounds. There-was' no added catalyst andno added solvent. The theoretical molecular'weight at-the end. ofthereactiomperiod :was i;

5 280. The: molal ratio of -:oxide toixcondensate was--96 -to'1.-'Conditionsas far as temperature and pressure .were concerned were thesameas in previous-examples. The "time period wasslightly longer, towit, 4: hours. Thereaction unquestionably began to slow' upvsomewhat.

...Example .5c

Theoxyethylation contin-ued with'the introduction: of another-10.56pounds of ethylene oxide. :Noea'ddedsolvent was introduced and,likewise, no 'added catalystwas introduced. The theoretical molecular:Weight at theend of the agitation period was 6336, and the molalratio-of oxide to resin condensate was 124 to 1. The time period,however, had increased to 5 hours even though the operating temperatureand pressureremained the same as in previous example.

Example 60 The-same procedure wasfoll'owed'as;,in:.the;previous-.sixexampleswithout the addition rof rmore caustic: or more solvent..The total amount of oxide-introducedat the end of the period. was 72.93pounds. 'jThe theoretical .molecular'weight at the e'ndnof the.oxyalkylation period -was 84.48. The time-required for theoxyethylation was a bit longerthan in the previous: step, towit,6shours.

. Example 80 This. Was. the final oxyethylation. in...this particular.series. There was no addedsolvent-and .no' addedrcatalyst. The totalamount of oxidezadded atthe end of this step was 85.48 pounds.. Thetheoretical molecular weight was.9.604. The:molal. ratio .of oxideto'resin condensate was- 192. .lConditions as faras temperatureand-pressure were concerned were the, same as .in the .previous ex.amples and the. timerequired for'oxyethylation :was the sameas inExample 71:, preceding; to wit-, 6ahours.

"The same procedure as described. inthe previous ex- .amples wasemployed in connection witha numbenof -the other condensatesdescribedpreviously. All-"these ,data have been;presented in tabular form ina.series of four tables, Tables llland IV, V and VI.

In substantially every case a -.gallon.autoclave...was employed,although in some instances the initial oxyethylation was started in a15-gallon autoclave and sene.

14 rthen transferred to a .25figallonrautoclave. ,This;is. im-:matemalabut. happenedrtobe a matter ofaconnenience .only. Then-solvent-used-in all cases-was xylene. -.The

. catalyst .-used. was .finelypowdered caustic soda.

. .'Referring-no.w to Tables III and IV, it will be noted that compounds16 .through=40c were-obtained bymthe -use'of ethylene-oxide, whereas 41cthrough-c wererob- -ta-ined-by the use of 'propyleneoxide alone.

Thus,-in reference to TableHI it is to benotedas follows.

The examplenumber ofeach compound is indicated-in the first column.

. The identity of the oxyalkylation-susceptible com- .poundyto wit,theresin condensate, is tindicated-inthe second column.

The amount of-condensate is shown in the". third col- .u-rnn.

Assuming that ethylene oxide alone is employed as happens, to be thecase in Examples 12 through-.400; the amountof oxidepresent in theoxyalkylation derivative is shown in. column 4,-although:in the initialSiCpwSiIlCBDO oxide is present there isv a, blank.

When ethylene oxide is used exclusively .the-Sth-col- -umn is blank.

6 The 6th columnshows. the amountofpowderedrcaustic :soda-vused as acatalystand-the "7th column-"shows the amount ofsolvent. employed.

1' The 8th column canvbedgnored where a singlezoxide was employed.

The--9th column-shows- -the theoretical molecular "weight at the end oftheoxyalkylation period.

The 10th column states the amount of condensate pres- -.ent imthe;reaction" mass at the'end ofthe period.

ASLPOlHtfid out previously,xinx this particular seriesthe-amount.of-reactrontmass-withdrawn for examination was sorrsmall thatrte-.waswrgnoredand for this reasontherresin condensate in, columnlOcoincides with the 'figure' inzcol- ..umn3.

.;Column 11 shows the;am0unt'0f ethylene oxidenem- :cployed' in tthereaction mass: at'thezend of the-particular :perrod.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.Column-l4 sh0Ws-the-amountof" solvent at the end of the reactiomperiod.

Column. 1 5 shows the'molalfratio of :ethylene oxide to .condensate.

Column 16-can: be ignored forthe reason that no propylene oxide wasemployed.

Referringenowto-Table VI. It is to :benoted that the :first column:refers to.Examples 10, 2c, 30, etc.

The second column gives the maximum temperature employed during theoxyalkylation step andthe third column! gives the maximum pressure.

" The fourth column gives-the tirnexperiod employed.

Th'elast three columns show solubility tests by shaking arsmalhamount ofthe compound, including .the solvent :present,--with several volumes ofw-aten xylene and kero- It sometimes happens that althoughv xylene incomparatively,.srnallzamounts willdissolve vingthe concentratedmaterial, when the concentrated material in turn is diluted with.xy1eneseparation takes'place.

Referringrto .Table IV, Examples 41c through 800 are the counterpartsof. Examples 1c through 400, except that rthe oxide. employed ispropylene oxide instead of ethylene oxide. 1Therefore,.as'explainedpreviously, fourcolumns are blank, to -wit,- columns 4, 8, 11 and 15.

Reference is nowmade to .Table V. It is to-be noted :these compounds aredesignated by "(1 numbers, 1d,

. 2d, 3d, etc.,through and: including 32d. They are derived, in turn,from compounds in the 0 series, for example, 350, 39c, 53csand 62c.Thesecompounds in- .volve" the; use of both ethylene oxide andpropyleneoxide.

=Since compounds 10 through 400 were obtained by the wuse of ethyleneoxide, it is obvious that those:obtained fr.om.35c, through 39e,,involve the use of ethylene oxide first, and propyleneoxide. afterward.Inversely, those compounds obtainedfrom 53c and 620 obviously came fromatprior series .in' whichpropylene oxide was used tion stopped at thepoint designated instead of being carried further as may have been thecase in the original oxyalkylation step. Then oxyalkylation proceeded byusing the second oxide as indicated by the previous explanation, to wit,propylene oxide in 1d through 16d, and ethylene oxide in 17d through32d, inclusive.

In examining the table beginning with 1d, it will be noted that theinitial product, i. e., 350, consisted of the reaction product involving10.5 pounds of the resin condensate, 15.84 pounds of ethylene oxide, 1.0pound of caustic soda, and 8.8 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers tothe total amount of catalyst, i. e., the catalyst present from the firstoxyalkylation step plus added catalyst, if any. The same is true inregard to the solvent. Reference to the solvent refers to the totalsolvent present, i. e., that from the first oxyalkylation step plusadded solvent, if any.

In this series, it will be noted that the theoretical molecular weightsare given prior to the oxyalkylation step 20 and after the oxyalkylationstep, although the value at the end of one step is the value at thebeginning of the next step, except obviously at the very start the valuedepends on the theoretical molecular weight at the end of the intialoxyalkylation step; i. e., oxyethylation for 1d through 16d, andoxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of bothoxides to the resin condensate are included.

The data given in regard to the operating conditions is substantiallythe same as before and appears in Table If de- 35 Obviously, in the useof ethylene oxide and propylene oxide in combination one need not firstuse one oxide and then the other, but one can mix the two oxides andthus obtain what may be termed an indiiferent oxyalkylation, i. e., noattempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then usepropylene oxide, and then go back to ethylene oxide; or, inversely,start with propylene oxide, then use ethylene oxide, and then go back topropylene oxide; or, one could use a combination in which butylene oxideis used along with either one of the two oxides just mentioned, or acombination of both of them.

The colors of the products usually vary from a reddish amber tint to adefinitely red, and amber. The reason is primarily that no effort ismade to obtain colorless resins initially and the resins themselves maybe yellow, amber, or even dark amber. Condensation of a nitrogenousproduct invariably yields a darker product than the original resin andusually has a reddish color. The solvent employed, if xylene, addsnothing to the color but one may use a darker colored aromatic petroleumsolvent. Oxyalkylation generally tends to yield lighter colored productsand the more oxide employed the lighter the color of the product.Products can be prepared in which the final color is a lighter amberwith a reddish tint. Such products can be decolorized by the use ofclays, bleaching chars, etc. As far as use in demulsification isconcerned, or some other industrial uses, there is no justification forthe cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present iscomparatively small and it need not be removed. Since the products perse are alkaline due to the presence of a basic nitrogen, the removal ofthe alkaline catalyst is somewhat more diflicult than ordinarily is thecase for the reason that if one adds hydrochloric acid, for example, toneutralize the alkalinity one may partially neutralize the basicnitrogen radical also. The preferred procedure is to ignore the presenceof the alkali unless it is objectionable or else add a stoichometricamount of concentrated hydrochloric acid equal to the caustic sodapresent.

TABLE III Composition before Composition at end Molal ratio to o-s*Ethl. Propl. 0am Sol- Theo. Theo. o-s* Ethl. Prppl. Gata- Solcmpd.,oxide, oxide, lyst, vent, rnol. mo]. cmpd., oxide, oxide, lyst, vent,

lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. Ethyl Proploxide oxide *Oxyalkylation-susceptible.

TABLE IV Composition before Composition at end F N S 14015] ratio tocmpd o-s* Ethl. Propl. Cata- Sol- Theo. Theo. 0-s* Ethl. Propl. cm- 801-5111 0011991153 EX cmpd., oxide, oxide, lyst, vent, mol. mol. cmpd.,oxide, oxide, lyst, vent, NIL lbs. lbs. lbs. lbs. lbs. Wt. Wt. lbs. lbs.lbs. lbs. lbs. Ethyl' Prom oxide oxide 10.56 1.0 8,8 2,112 10.56 10.561.0 8.8 18.2 10.56 10.56 1.0 8.8 3.168 10.56 21.12 1.0 8.8 36.4 10.5621.12 1.0 8.8 4,224 10.56 21.68 1.0 8.8 54.6 10. 56 31. 68 1. 0 8.8 5.280 10. 56 42. 24 1.0 8. 8 72.8 10.56 42. 24 1. 0 8. 8 6, 336 10. 56 52.80 1. 0 8. 8 91. 10. 56 52. 80 1. 5 8. 8 8, 348 10. 56 73. 92 1. 5 8. 8127. 10. 56 73.92 1. 5 8. 8 10. 56 95.04 1. 5 8. 8 163. 10. 56 95.04 1.5 8. 8 10. 56 116. 16 1. 5 8. 8 200. 12.56 1,2 9.6 12.56 12.56 1.2 9.621. 12. 56 12.56 1. 2 9. 6 12. 56 25.12 1. 2 9. 6 43. 12.56 25.12 1.29.6 12.56 37.68 1.2 9.6, 64. 12. 56 37. 68 1. 2 9. 6 12. 56 50.24 1. 29. 6 86. 12. 56 50. 24 1. 2 9. 6 12. 56 62. 80 1. 2 9. 6 108. 12. 5662.280 1. 2 9. 6 12. 56 87. 92 1. 2 9. 6 151. 12. 56 87. 92 1. 2 9. 612. 56 113.04 1. 2 9. 6 194. 12. 56 113104 1.2 9. 6 12. 56 138. 16 1. 29. 6 238. 10. 84 1. 0 8. 8 10. 84 10.84 1.0 8. 8 18. 10.84 10. S4 1. 08. 8 10. 84 1. 0 8. 8 37. 10. 84 21.68 1. 0 8. 8 10. 84 1. 1. 0 8. 8 56.10. 84 .32. 52 1. 0 8.8 10. 84 1. 0 8. 8 74. 10.84 1. 0 8. 8 10. 84 1. 08. 8 93. 10. 84 1. 0 8. 8 10.84 1. 0 8. 8 130. .84 1. 0 8. 8 10. 84 1. 08. 8 170. 10. 84 1.0 8. 8 10.84 1. 0 8. 8 205 1. 0 10. 2 12. 84 6 10. 222. 1. 0 10. 2 12. 84 .6 l0. 2 44;. 1.0 10.2 12.84 .6 10. 2 6.6, 1. 010. 2 12.84 51. 6 10. 2 88. 1.0 10. 2 12. 84 6 10. 2 110. 1.25 10.212.84 .9 10.2 154. 1. 10. 2 12. 84 .9 10. 2 199. 1.25 10. 2 12. 84 9 10.2 244. 1. 0 8. 8 10. 56 1. 0 8. 8 9. 1. O 8. 8 10. 56 10. 56 1. 0 8. 818. 1.0 8.8 10. 56 15.84 1.0 8.8 27; 1. 0 8. 8 10. 56 21. 12 1. O 8. 836. 1. 0 8. 8 10. 56 26. 1. 0 8. 8 45. 1. 0 8. 8 10. 56 36.96 1.0 8. 863. 1.05 8. 8 10. 56 47.52 1. 25' 8. 8 81. 1. 25 8. 8 10. 56 58. 08 1.25 8. 8 100.

Oxyalkylationsusceptible.

TABLE V Composition before Composition at end Molal ratio .to EL 2'?o-s* Ethl. Prop]. om s01- Theo. Theo. 0-s* Etlil. Propl. Oata- Sol 5111mndensate cmpd., oxide, oxide, lyst, vent, mol. mol. cmpd oxide, oxide,lyst, vent. N2 lbs. lbs. lbs. lbs. lbs. wt. Wt. lbs. lbs. Ilbs. lbs.lbs. Ethyl PmpL oxide oxide 10. 56 15. 84 1. 0 8. 8 2, 640 3, 168 10. 5615. 84 5. 28 1. 0 8. 8 36 9. l 10. 56 15. 84 5. 28 1.0 8. 8 3, 168 3,696 10. 56 15.84 10. 56 1.0 8. 8 36 18.2 10. 56 15. 84 10. 56 1. 0 8.83, 696 4, 224 10. 56 15. 84 15. 84 1. 0 8. 8 36 2,7. 3 10:56 15. 84 15.84 1.0 8. 8 4, 224 4, 752 10. 56 15.84 21. 12 1. 0 8. 8 36 36.4 10. 5615. 84 21.12 1. 5 8. 8 4, .752 5, 380 10. 56 15.84 26. 40 1. 5 8. 8 3645. 5 10:56 15. 84 26. 40 1. 5 8. 8 5, 380 5, 908 10. 56 15. 84 31.68 1. 5 8. 8 36 54. 6 10. 56 15. 84 31. 68 1. 5 8. 8 5, 908 6, 438 10.56 15. 84 36. 96 1. 5 8. 8 36 63. 7 10. 56 15. 84 36 96 1. 5 8. 8 6, 4386, 964 10. 56 15. 84 42. 24 1. 5 8. 8 36 72. 8 1O. 56 36. 96. 1. 5 8. 84, 752 5, 280 10. 56 36. 96 5. 28. 1. 5 8. 8 84 9. 1 10. 56 36.96 5.28 1. 5 8. 8 80 5, 808 10. 56 36.96 10. 56 1. 5 8. 8 84 18.2 10. 5636.96 10. 56 1. 5 8. 8 5,808 6, 336 10. 56 36.-96 15. 84 1. 5 8. 8 8427.3 10.56 36.96 15.84 1.5 8.8 6,336 7,392 10.56 36.96 26.40 1.5 8.8- 8445.5 10. 56 36. 96 26. 40 1. 5 81 8 7, 392 8, 448 10. 56 36. 96 36.96 1. 5 8. 8 84 63. 7 10.56 36.96 36.96 1.5 8.8 8,448 9,504 10.56 36.9647.52 1.5 8.8 84 81.9 10. 56 36. 96 47. 52 1. 5 8. 8 9, 504 10, 560 10.56 36. 96 58.08 1. 5 8. 8 84 10.0. 1 10. 56' 36 96 58.08 1. 5 8. 8 10,560 11,616 10. 56 36.96 68. 64 1. 5 8. 8 84 118.3 12. 56 62. 80 1.8 9. 67, 836 8, 468 12. 56 6. 28 62. 80 l. 7 9. 6 14. 3 108.0 12. 56 6. 28 62.80 1. 7 9. 6 8, 464 9, 092 12. 56 12. 56 62. 80 1. 7 9. 6 28. 6 108.0'12. 56 12. 56 62. 80 1. 7 9.6 9, 092 10,348 12. 56 18. 84 62. 80 1. 79. 6 42. 8 109.0 .12. '56 18. 84 62.80 1. 7 '9. 6 10,348 11, 604 12. 5631.40 62. 80 1. 7 9. 6 71. 4 108.0 12. 56 31.40 62.80 1.7 9. 6 11,60412,860 12.56 43 96 62 80 1. 7 9.6 99.9 108.0 12.56 43. 96 62.80 1. 7 '9.6 12, 860 14,11 12.56 56 .52 62 80 1. 7 9. 6. 128. 5 108. 0 12.56 56.5262.80 1. .7 9. 6 14,116 15, 372 12.56 69 08 62 80 1.7 9. 6 157.0 108.012.5.6 69. 08 62.80 i 1. 7 9.6 15,372 16, 628 12.56 81 64 62 80 1.7 9. 6185. 8 108. 0 10.84 75.88 1. 5 8.8 8, 672 9,214 10. 84 5 42 88 1.5 8. 8,12.3 130.-9 10.84 5. 42 75:88 1. 5 8.8' 9, 214 9, 756 10.84 10 84 7588 1. 5 8. 8 24.6 130.9 10184 10.84 .75.- 88 1. 5 8'. 8 9, 756 10, 29810. 84 16 26 75 88 1. 5 8. 8 36. 9 130. 9 10. 84 16. 26 75. 88 1. 5 8. 810, 298 11, 382 10. 84' 27 10 75.88 1. 5 8. 8 61.5 130.9 10.84 27.1075.88 1. 5 8.8 11,382 12,466 10.84 37 94 75.88 1. 5 8. 8 86.1 130.910.84 37.94 75; 88 1.5 8.8 13, 466 13, 550 10. 84 48 78 75.88 1. 5 8. 8110. 7 130.9 10.84 48. 78 y 75. 88 1. 5 8. 8 13, 550 14, 634 10. 84' 7588 75. 88 1. 5 8. 8 135. 3 130.-9 10.84 59. 62 .75. 88 1. 5 8. 8 14, 63416,626 10. 84 75 88 75.88 1. 5 8. 8 172.0 130.9

'Oxyalkylation-susceptible.

19 20 TABLE VI TABLE VI-Oontinued s 1 bil't Time u 1 y Ex t Max TimeSolubility hrs. No. i pres! hrs.

Water Xylene Kerosene S Water Xylene Kerosene 3% 24d. 130-135 20-25 4 12511"... 125-130 20-30 V2 26d..- 125-130 20-30 1 a s 4 2711..." 125-13020-30 1 5 2811.- 125-130 20-30 1% 5 29d. 125-130 20-30 2 6 3011 125-13020-30 3 E 6 3111..... 125-130 20-30 4% B 3 1 211... 125-130 20-30 5 3 31 Insoluble. 3% 2 Emulsifiable. 5 Soluble. 6 4 Dispersible. 6 5Emulsifiable to insoluble. 4 fi Emulsifiable to soluble. 3 (3) 1 E1;PART 5 g I In practicing the present process, the treating or de- 3%mulsifying agent is used in the conventional way, well 5 2 known to theart, described, for example, in Patent 2 8 3 2,626,929, dated January27, 1953, Part 3, and reference 2% is made thereto for a description ofconventional pro- 3 i cedures of demulsifying, including batch,continuous, and 3 E down-the-hole demulsification, the processessentially in- 4 volving introducing a small amount of demulsifier intog f; a large amount of emulsion with adequate admixture 1 1 with orwithout the application of heat, and allowing 2 the mixture to stratify.g In many instances the oxyalkylated products herein 1045 4 11 specifiedas demulsifiers can be conveniently used with- 10-15 4% out dilution.However, as previously noted, they may be i832 2 diluted as desired withany suitable solvent. For in- 1045 3 2 1 stance, by mixing 75 parts byweight of an oxyalkyl- 10-15 3 ated derivative, for example, the productof Example 18:12 2 20 with 15 parts by weight of xylene and 10 parts by10.15 4 1 weight of isopropyl alcohol, an excellent demulsifier 10-15 4is obtained. Selection of the solvent will vary, depend- 218 i ing uponthe solubility characteristics of the oxyalkylated 1% 1 1 1 product, andof course will be dictated in part by eco- 0) nomic considerations, i.e., cost. ilg 8 g As noted above, the products herein described may 3 l1 a be used not only in diluted form, but also may be used E admixedwith some other chemical demulsifier. A mixgjg 1% ture which illustratessuch combination is the follow- 5- 31 Oxyalkylated derivative, forexample, the product of as g g E? Example 20, 20%; 3 1; a; (a): Acyclohexylamine salt of a polypropylated naphthalene 5 38 g monosulfonicacid, 24%; H5 1% (I) (5) An ammonlurn salt of a polypropylatednaphthalene 10.15 2 1 a 1 monosulfonlc acid, 24% 15 2 A sodium salt ofoil-soluble mahogany petroleum g sulfonic acid, 12%; 10.15 3 1 1 a Ahigh-boiling aromatic petroleum solvent, 15%; 5 3% (g) (g)- Isopropylalcohol, 5%.

f 2,; The above proportions are all weight percents. 15 20 1% 1 (a 1Having thus described my invention, what I claim as l520 1A (1) (g) (i)-new and desire to obtain by Letters Patent, is h1g8 g 3 E 1. A processfor breaking petroleum emulsions of the 15-20 4 water-in-oil typecharacterized by subjecting the emulsion 1520 (i) (Z) (2% to the actionof a demulsifier including the products ob- 33 2 E 8 8: tained in theprocess of first condensing (a) an oxy- 15-20 2% alkylation-susceptible,fusible, non-oxygenated organic ggg i f 2 solvent-soluble,water-insoluble, low-stage phenolaldehyde 1540 2% 8 $1; 21;: resinhaving an average molecular weight correspond- 1520 ing to at least 3and not over 6 phenolic nuclei per P 38 3 i (a) resin molecule; saidresin being difunctional only in regard 2 20-25 (a a 1 tomethylol-forrnlng reactiv ty, said resin be ng derived by 2OZ5 1 g) (3)(9- reaction between a difunctional monohydric phenol and 20-25 1 a analdehyde having not over 8 carbon atoms and re- 2 -2 M u o. 20-25 3active toward sald phenol; said resm being formed in i g 3 i thesubstantial absence of trifunctional phenols; said 20 25 5 8 phenolbeing of the formula 20-25 OH 20-25 20-25 20-25 20-25 1% R 20-25 2%20-25 3% See at end in which R is an aliphatic hydrocarbon radicalhaving 21 at least 4 and not more than 24 carbon atoms and sub stituted111 the 2,4,6- position; (b) a basic n'onhydroxylated secondarym'onoamine having not more than 32 carbonatoms in any group attached LOEhe amino nitrogen atom, and formaldehyde; said condensation reactionbeing conducted at a temperature sufficiently high to eliminate waterand below the py-rolytic point of the reactants and resultants ofreaction; and with the proviso that the resinous condensation productresulting from the process be heat-stable and oxya-lkylatiomsuseeptible;followed by an oxyalkylation step by means of an alpha-beta alkyleneoxide having not more than 4' carbon atoms and selected from the classconsisting of ethylene oxide, propylene oxide, 'butylene oxide, glycideand methylglycide.

2. A process for breaking petroleum emulsions of the water-in oil'typecharacterized by subjecting the emulsion to the action of ademulsifier including the products obtained intheprocess-of firstcondensing (a) anoxyalkylation susceptible, fusible, non-oxygenatedorganic solventsoluble, water-insoluble, low-stage phenol-aldehyde resinhavingan average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin-being difunctionalonly in regard to methylolforming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and an aldehydehaving not over -8 carbon atoms and reactive toward said phenol; saidresin being formed in the substantial absence of trifunctional phenols;said phenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (-b) a basic nonhydroxylatedsecondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogen atom, and (c) formaldehyde; saidcondensation reaction being conducted at a temperature sufliciently highto eliminate water and below the pyrolytic point of thereactants andresultants of reaction; with the proviso that the condensation reactionbe conducted so as to produce'a significantportion of the resultant inwhich each of the three reactants has contributed part of the ultimatemolecule by virtue of a formaldehyde-derived methylene bridge connectingthe amino nitrogen atom with -a resin molecule; with the further provisothat the ratioof reactants beapproximately l, 2 and 2 respectively; andwith the final proviso that the resinous condensation product resultingfrom the process be heat-stable and -oxyalkylation-susceptible; followedby an oxyalkylation step by means of analpha-beta alkylene oxide havingnot more than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butyl'ene oxide, glycide andmethylglycide.

3. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products'obtained in the process of first condensing (a)an oxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difuncticnal onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatichydrocarbonradical having at-least 4 and not more than 24 carbon atoms andsubstituted-.inthe 2,4,6 position;'(b) a basic nonhydroxylated secondarymo'noamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen 1 atom, and (0) formaldehyde; said condensationreaction be- 22?; ing conducted at a temperature sufficiently nigh 'itOeliminate water and belowth'e pyrolytic point ofthe reactants andresultants of reaction, with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants has contributed part of theultimatemolecule by virtue of a formaldehyde-derived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the added provisothat the ratio of reactants be approximately l, 2 and 2, respectively;with the further proviso that said procedure involve the use of asolvent; and with the final proviso that the resinous condensationproduct resulting from the process be heatstable andoxyalkylationasusceptible; followed by an oxyalkyl-ation step by meansof an alpha-beta alkylene oxide having not more than. 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylglycide.

4. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyethylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage-phenol-formaldehyde resinhaving an average molecular weight-corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin beingdifunct-ional only in regard to methylol-forming reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andformaldehyde; said resin being formed in the substantial absence oftrifunctional phenols; said phenol being of the formula in which R is analiphatic "hydrocrabon radical having at least 4 and not more than 24carbon atoms and substituted in the 2,4,6 position; ('b) a basicnonhydroxylated secondary monoamine having not more than 32 carbon atomsin any group attached to the amino nitrogen atom, and (c formaldehyde;'said condensation reaction being conducted at a temperature.sufficiently high to eliminate water and below the pyrolytic point ofthe reactantsand resultants-of reaction, with the proviso thatthecondensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants hascontributed part of the ultimate molecule by virtue'of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; with the added proviso that the ratio ofreactants be approximately 1, 2 and 2, respectively; with the furtherproviso that said procedure involve the use-of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by anoxyal-kylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide.

5. A process for breaking petroleum emulsions-of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyethylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard'to methylol-forming reactivity; said resin being'derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than 14 carbon atomsand substituted in the 2,4,6 position; (b) a basic nonhydroxylatedsecondary monoamine having not more than 32 carbon atoms in any groupattached to the amino nitrogen atom, and (c) formaldehyde; saidcondensation reaction being conducted at a temperature sufiiciently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction, with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants has contributed part of the ultimatemolecule by virtue of a formaldehyde-derived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the added provisothat the ratio of reactants be approximately 1, 2 and 2, respectively;with the further proviso that said procedure involve the use of asolvent; and with the final proviso that the resinous condensationproduct resulting from the process be heatstable andoxyalkylation-susceptible; followed by an oxyalkylation step by means ofan alpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylyglycide.

6. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyethylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 5 phenolic nuclei per resin molecule; to methylol-formingreactivity; said resin being derived by reaction between a difunctionalmonohydric phenol and formaldehyde; said resin being formed in thesubstantial absence of trifunctional phenols; said phenol being of theformula in which R is an aliphatic hydrocarbon radical having at least 4and not more than 14 carbon atoms and substituted in the 2,4,6 position;(b) a basic nonhydroxylated secondary monoamine having not more than 32carbon atoms in any group attached to the amino nitrogen atom, andformaldehyde; said condensation reaction being conducted at atemperature sulficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction, with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; with the added proviso that the ratio ofreactants be approximately l, 2 and 2, respectively; with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide.

7. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyethylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at said resin being difunctional only inregard least 4 and not more than 14 carbon atoms and substitut ed in the2,4,6 position; (b) a basic nonhydroxylated secondary monoamine havingnot more than 32 carbon atoms in any group attached to the aminonitrogen atom, and (c) formaldehyde; said condensation reaction beingconducted at a temperature above the boiling point of water and belowC., with the proviso that the condensation reaction be conducted so asto produce a significant portion of the resultant in which each of thethree reactants have contributed part of the ultimate molecule by virtueof a formaldehyde-derived methylene bridge connecting the amino nitrogenatom with a resin molecule; with the added proviso that the ratio ofreactants be approximately 1, 2 and 2, respectively; with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide.

8. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyethylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 5 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is apara-substituted aliphatic hydrocarbon radical having at least 4 and notmore than 14 carbon atoms and substituted in the 2,4,6 position; (b) abasic nonhydroxylated secondary monoamine having not more than 32 carbonatoms in any group attached to the amino nitrogen atom, and (0)formaldehyde; said condensation reaction being conducted at atemperature above the boing point of water and below 150 C., with theproviso that the condensation reaction be conducted so as to produce asignificant portion of the resultant in which each of the threereactants have contributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; with the added proviso that the ratio ofreactants be approximately 1, 2 and 2, respectively; with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide.

9. The process of claim 1 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sulficient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of Water.

10. The process of breaking petroleum emulsions as defined in claim 1wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

11. The process of claim 10 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufiicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

12. The process of claim 2 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are suflicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of Water.

13. The process of breaking petroleum emulsions as defined in claim 2wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and proplyene oxide in combination.

14. The process of claim 13 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal Weight of xylene are sufficient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

15. The process of claim 3 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufiicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

16. The process of breaking petroleum emulsions as defined in claim 3wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

17. The process of claim 16 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufiicient to produce anemulsion when said xylene solution is shaken vigorously with l to 3volumes of water.

18. The process of claim 4 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufficient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

19. The process of breaking petroleum emulsions as defined in claim 4wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

20. The process of claim 19 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are suflicient to produce anemulsion when said Xylene solution is shaken vigorously with 1 to 3volumes of water.

21. The process of claim 5 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufiicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

22. The process of breaking petroleum emulsions as defined in claim 5wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

23. The process of claim 22 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are suflicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

24. The process of claim 6 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufiicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

25. The process of breaking petroleum emulsions as defined in claim 6wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

26. The process of claim 25 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sulficient to produce anemulsion when said xylene solution is shaken vigorously with l to 3volumes of water.

27. The process of claim 7 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are sufficient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

28. The process of breaking petroleum emulsions as defined in claim 7wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

29. The process of claim 28 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are suflicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

30. The process of claim 8 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a mem ber of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are suflicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

31. The process of breaking petroleum emulsions as defined in claim 8wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

32. The process of claim 31 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are suificient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,031,557 Bruson Feb. 18, 1936 2,499,365 De Groote et a1. Mar.7, 1950 2,499,368 De Groote et a1. Mar. 7, 1950 2,542,011 De Groote eta1. Feb. 20, 1951

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSIONS TO THE ACTION OF A DEMULSIFIERINCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF FIRST CONDENSING (A)AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATE ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLADEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLYIN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESINBEING FORMED IN THE SUBSTANTIAL ABSECNE OF TRIFUNCTIONAL PHENOLS; SAIDPHENOL BEING OF THE FORMULA